Design of Chiral Kink Atoms on Single Gold Nanoparticle for the Effiecient Electrocatalysis of Glucose

Equipping heterogeneous catalysts with catalytic functions of natural enzymes can increase the efficiency and selectivity of the catalysts and potentially also enable the enantioselective catalysis of nonbiological reactions. In contrast to the progress made with the pioneering examples of homogeneous and single-atom catalysts afforded by coordination and ligand field tuning, the progress in the rational engineering of metallic and inorganic electrocatalysts for electrochemical reactions has been limited. Representative examples include molecular imprinting on metallic surfaces applied to asymmetric electrosynthesis of optically active alcohols from aromatic ketones and the introduction of organic modifiers in electrocatalysts to provide additional binding interactions for intermediates in the carbon dioxide reduction reaction. On the basis of the current understanding of the importance of local geometry and atomic arrangements of electrocatalysts, we investigate the correlation between metallic surfaces defined by high-Miller-index planes and electrocatalytic selectivity and explore the potential of using kink-controlled nanoparticles as a platform to design catalysts with enzyme-like functions. We aim to control the kink/step density and the three-dimensional (3D) coordination at active kink sites.<br/>Enantioselective oxidation of organic molecules by heterogeneous electrocatalysts is challenging because of the difficulty to control the asymmetric structures of the active sites on the electrodes. Here, we show that the distribution of chiral kink atoms on high-index facets can be precisely manipulated even on single gold nanoparticles; and this enabled stereoselective oxidation of hydroxyl groups on various sugar molecules. As a result, the lower limit of detection for β-D-glucose was 1 nM, a lower value than for any of the synthetic catalysts reported to date, and the device sensitivity was comparable to that of the current sensing device containing glucose oxidase. This study provides a synthetic platform to translate the biological principles of designing geometrically structured active sites to electrochemical devices by controlling nanoparticle kink sites, specifically on concave high-index facets.